CN102823046A - High performance flow battery - Google Patents
High performance flow battery Download PDFInfo
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- CN102823046A CN102823046A CN2011800168736A CN201180016873A CN102823046A CN 102823046 A CN102823046 A CN 102823046A CN 2011800168736 A CN2011800168736 A CN 2011800168736A CN 201180016873 A CN201180016873 A CN 201180016873A CN 102823046 A CN102823046 A CN 102823046A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/70—Arrangements for stirring or circulating the electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
High performance flow batteries, based on alkaline zinc/ferro-ferricyanide rechargeable (''ZnFe'') and similar flow batteries, may include one or more of the following improvements. First, the battery design has a cell stack comprising a low resistance positive electrode in at least one positive half cell and a low resistance negative electrode in at least one negative half cell, where the positive electrode and negative electrode resistances are selected for uniform high current density across a region of the cell stack. Second, a flow of electrolyte, such as zinc species in the ZnFe battery, with a high level of mixing through at least one negative half cell in a Zn deposition region proximate a deposition surface where the electrolyte close to the deposition surface has sufficiently high zinc concentration for deposition rates on the deposition surface that sustain the uniform high current density. The mixing in the flow may be induced by structures such as: conductive and non-conductive meshes; screens; ribbons; foam structures; arrays of cones, cylinders, or pyramids; and other arrangements of wires or tubes used solely or in combination with a planar electrode surface. Third, the zinc electrolyte has a high concentration and in some embodiments has a concentration greater than the equilibrium saturation concentration, i.e., the zinc electrolyte is super-saturated with Zn ions.
Description
The cross reference of related application
The application's case is advocated the U.S. Provisional Application case the 61/319th in submission on March 30th, 2010; No. 248 and the U.S. Provisional Application case the 61/322nd submitted on April 9th, 2010; No. 780 rights and interests, said U.S. Provisional Application case is all incorporated this paper into way of reference.
Technical field
The present invention relates to high performance electrochemical and learn battery and battery pack, and more particularly relate to the flow battery group.
Background technology
" greenization " of energy economy, regenerative resource (such as, wind energy and solar energy) expection of ever-increasing demand and use and (for example) plug-in hybrid vehicle and full electric vehicle increases sharply and makes distrbution network nervous day by day.High power capacity power storage technology (such as; The pumps water power technology) can be in the network load balance, the time that produces plays an important role to the time shift regenerative resource of using the peak period certainly; Yet; Geographical position and cost limit use, the especially use on regional level of said high power capacity power storage technology.
Existing high-capacity battery group technology (for example, the flow battery group) is too expensive for extensive employing, because the gained energy of carrying and/or the cost-effectively of power are much higher than the market price.Therefore there are unsatisfied in fact needs for low cost, high power capacity, high efficiency and high performance battery technology.
Summary of the invention
Embodiments of the invention provide high-performance flow battery group equipment and the method that is used to strengthen, charge, operate and use the flow battery group.High current density charge rate that various embodiment of the present invention provides and discharge rate are in approximate 70mA/cm
2To 400mA/cm
2In the scope, and more particularly be in 100mA/cm
2To 250mA/cm
2In the scope.
The embodiment of high-performance of the present invention, Alkaline Zinc/ferroferricyanide chargeable (" ZnFe ") flow battery group is based on the many improvement for prior art.These embodiment are applicable to that also bond electroplates other flow battery group of stored energy (such as ZnHBr; ZnBr; CeZn; And ZnCl).
First; The battery pack design has cell stacks; Said cell stacks comprise low resistance at least one positive half-cell anodal with at least one negative half-cell in the low resistance negative pole, wherein select positive electrode resistance and negative pole resistance with the even high current density on the acquisition entire cell stack region, promptly; Make resistance on the electrode enough low guaranteeing change in voltage less on the entire electrode, so uniform current flow out outside the electrode and on entire cell is piled up and flow.
Second; Mixing (this paper is also referred to as " two-forty mixings " and " high mixed ") with high level near the electrolyte stream of at least one half-cell of bearing in the Zn deposition region of deposition surface (for example flows through; Zinc species in the ZnFe battery pack); The electrolyte that wherein approaches deposition surface has sufficiently high zinc concentration, on deposition surface, to obtain to keep the deposition rate of even high current density.The mixing of electrolyte stream and flow is enough to support the mass tranfer coefficient of high current density and the uniform deposition in fact on the deposition surface of (for example) zinc at battery is provided to provide through design in the negative half-cell.In addition, some embodiment are designed to flow with the electric current less than limiting current zinc deposition to be provided, the non-dendrite morphology that the zinc that is wherein deposited has is intensive, adhere to.
The 3rd, zinc electrolyte has high concentration, and in certain embodiments, and the concentration of zinc electrolyte is greater than the balance saturated concentration, that is, and and the Zn ion over-saturation of zinc electrolyte.One or more a plurality of improvement in these improvement of different embodiments of the invention combination.
High mixed flow through the electrolyte stream of battery possibly be since in the parallel-plate passage higher fluid velocity cause.Yet the mixing in the flow can be by inducing such as following structure: conductive mesh and non-conductive mesh; Screen cloth; Band; Foaming structure; The array of cone, cylinder or pyramid; With other layout of line or pipe, said structure can use separately or use with smooth electrode surface combination.The electrolyte that the use of this class formation can allow to have laminar flow or have a turbulent flow is with higher or lower fluid velocity high mixed.In addition, be used for making the tranquil structure of turbulent flow can be included in the electrolyte flow pipeline that is right after after battery.
According to embodiments of the invention, the method that is used for operating the flow battery group can comprise to be made with the electrolyte stream of laminar flow regime or turbulent flow attitude high mixed through at least one the negative half-cell near the Zn deposition region of deposition surface.In addition, some embodiment comprise that deposition has Zn intensive, the non-dendrite morphology of adhering to.Can utilize the high mixed flow at the charging and/or the interdischarge interval of battery cell.
Description of drawings
Combining after accompanying drawing checks the following description of specific embodiment of the present invention, one of ordinary skill in the art will understand more of the present invention these with others and characteristic, wherein:
Fig. 1 is the sketch map of zinc redox flow batteries group;
Fig. 2 is the sketch map according to the zinc redox flow batteries group of some embodiments of the present invention;
Fig. 3 is the perspective schematic view according to the flow battery of some embodiments of the present invention;
Fig. 4 is according to some embodiments of the present invention, is contained in the perspective schematic view of the battery of the Fig. 3 in the framework;
Fig. 5 is according to some embodiments of the present invention, the schematic cross section of first instance of the cell arrangement of redox flow batteries group;
Fig. 6 is according to some embodiments of the present invention, the schematic cross section of second instance of the cell arrangement of redox flow batteries group;
Fig. 7 is according to some embodiments of the present invention, the schematic cross section of the 3rd instance of the cell arrangement of redox flow batteries group;
Fig. 8 is according to some embodiments of the present invention, and the instance of woven wire mesh hole characteristic is induced in the lip-deep mixing of flow battery group electrode;
Fig. 9 is according to some embodiments of the present invention, and the instance of non-woven wire mesh hole characteristic is induced in the lip-deep mixing of flow battery group electrode;
Figure 10 is according to some embodiments of the present invention, and the instance of line/pipe characteristic is induced in the lip-deep mixing of flow battery group electrode;
Figure 11 is according to some embodiments of the present invention, and the instance of array of cylinders is induced in the lip-deep mixing of flow battery group electrode;
Figure 12 is according to some embodiments of the present invention, and the instance of cone array is induced in the lip-deep mixing of flow battery group electrode;
Figure 13 is according to some embodiments of the present invention, and the instance of pyramid array is induced in the lip-deep mixing of flow battery group electrode; With
Figure 14 is the cross-sectional view according to the flow stratification characteristic of some embodiments of the present invention.
Embodiment
To describe embodiments of the invention in detail with reference to all figure now, said figure is provided as the illustrative example of some embodiments of the present invention, so that enable those skilled in the art to put into practice the present invention.Noticeable, the figure of hereinafter and instance also do not mean that category of the present invention be limited to single embodiment, but described to exchange or element shown in other embodiment of mode of some or whole elements be possible.In addition; Come under the situation of some element of embodiment of the present invention can partially or even wholly using known tip assemblies; With those parts of only describe understanding this type known tip assemblies essential to the invention, and will omit the detailed description of other part of this type known tip assemblies, in order to avoid the present invention is blured.In this manual, the embodiment of demonstration single component should not be regarded as restrictive; On the contrary, the present invention is intended to contain other embodiment that comprises a plurality of same components, and vice versa, really not so only if this paper conclusivelys show.In addition, only if likewise clearly set forth, otherwise the applicant is not intended to give uncommon or special meaning to any term in specification or claims.In addition, the known equivalent of the present and the future is contained in the present invention, and said equivalent is equivalent to the known tip assemblies that this paper mentions with the explanation mode.
Embodiments of the invention provide high-performance flow battery group equipment and the method that is used to strengthen, charge, operate and use the flow battery group.
Fig. 1 illustrates the instance of prior art redox flow batteries group 100.For example, referring to people's such as Wu Indian Journal of Technology, the 24th volume, in July, 1986,372-380 page or leaf.The flow battery group comprises positive half-cell 110 and negative half-cell 120, and positive half-cell 110 is separated by barrier film 130 respectively with negative half-cell 120.The electrolyte of half-cell is stored in groove 140 and the groove 150 and pumps through half-cell, as passing through shown in the arrow.Flow battery group shown in Fig. 1 is a Zn/Fe redox flow batteries group; Anodal electrolyte is the Fe compound, and negative pole electrolyte is zincate.Yet prior art flow battery group can not be with sufficiently high current density operation and the enough high next extensive energy storage that is used for of efficient viable economicallyly.The present invention provides the improvement for the flow battery group, and said improvement will allow low-cost but have high efficiency high current density operation.For example, some embodiments of the present invention will provide the redox flow batteries group, and the density of charging current of said redox flow batteries group is 70mA/cm
2, 80mA/cm
2, 90mA/cm
2, 100mA/cm
2, 125mA/cm
2, 150mA/cm
2, 200mA/cm
2With in addition higher.
Alkaline Zinc/the ferroferricyanide of some embodiments of the present invention (" ZnFe ") rechargeable battery group system is intended to be used for megawatt energy storages such as public power supply facilities load balancing, Steam Generator in Load Follow, zone adjusting service, power transmission and distribution extension application, wind energy and solar energy integrated application and uses; The energy storage capacity of said application from several minutes (such as, 15 minutes) to up to 24 hour duration with surpass 24 hour duration.The ZnFe battery pack is a mixed oxidization reducing solution galvanic battery group, and wherein active material (zinc oxide and sodium ferrocyanide) is stored in the accumulator tank of outside batteries and is sent to the site of electrochemical reaction as the saturated solution in the NaOH electrolyte.
Between charge period, energy is with the stored in form that is deposited on the zinc metal on the zinc electrode substrate and be stored as the ferricyanide that the anodic oxidation through the hydroferrocyanate reactant forms.When load need require, can simultaneously the ferricyanide ion be reduced into hydroferrocyanate to form zinc oxide through anodic solution zinc, and absorb energy from battery.Reversible and the tool selectivity of these process height, thus the operation of battery is had the following advantages: high cycle efficieny, high cell voltage, certainly load to isolate or self-isolation at full capacity less than random rotation time and switching time of 5ms.
Especially when the operating current density during the charging (deposition) increased, prior art flow battery group especially had the problem of dendrite formation based on the flow battery group of Zn.For example, the zinc dendritic crystal maybe be during deposition (charging) process in based on the battery pack of zinc because a variety of causes formation.The zinc dendritic crystal possibly have problems in the battery pack based on zinc, and said problem comprises that performance reduction, battery short circuit and operation lifetime reduce, and all said problems can increase the valid function cost.
Embodiments of the invention will be used to the maintainable operating current density that charges the battery and discharge through increase, reduce or minimize the growth of dendritic crystal, improve the performance (thereby reducing running cost) of zinc flow battery group and other flow battery group.For given flow battery group rated power; The flow battery group embodiment that is particularly useful for the electrical network memory application of the present invention generally will have approximate power output and approximate energy output or the discharge period in 5 minutes to 15 minutes to 24 hours that is in 5kWh to the 600MWh scope that is in 20kW to 25MW and bigger scope, but can use higher and lower power output and energy to export.Define charging interval and discharge time substantially by the application market of particular fluid flow battery pack product.Be 15 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 16 hours and 24 hours typical discharge time.The ratio of charging interval and discharge time generally is in 2 to 1 or 1 to 1 or 1 to 2 the scope, wherein approximate 1 to 1 charge and discharge ratio ideal comparatively.
The embodiment of high-performance flow battery group of the present invention (for example, ZnFe flow battery group) is based on the many improvement for prior art, and said improvement will allow with the high current density operation and/or reduce battery pack integrated operation cost.
First; The battery pack design has battery; Said battery comprise low resistance at least one positive half-cell anodal with at least one negative half-cell in the low resistance negative pole, wherein select positive electrode resistance and negative pole resistance with the even high current density on the acquisition cell stacks zone, promptly; Make the resistance on the electrode enough low to guarantee change in voltage less on the electrode; Therefore uniform current flows out outside the electrode and flows at least one zone of battery that (for example, change in voltage is usually less than 5mV to 10mV, and wherein the resistance on the battery is at operating current density 100mA/cm
2The following loss that produces less than 200mV, corresponding to current density change less than 20%).Battery usually together assembled in series become cell stacks, said cell stacks comprises a plurality of batteries.Be electrically connected the form that can be bipolar electrode or other electrode design between the battery in the cell stacks, said other electrode design comprises uses lead with the battery series connection and/or be connected in parallel together, to make cell stacks.Usually a plurality of cell stacks of combination make battery pack system.
Second; The electrolyte that two-forty is mixed (for example; Zinc species in the ZnFe battery pack) flow rate is through inducing near at least one the negative half-cell in the Zn deposition region of deposition surface; Wherein electrolyte solution has sufficiently high zinc concentration, on deposition surface, to obtain to keep the deposition rate of the even high current density on all batteries in fact on the battery or in the cell stacks.Flow in the negative half-cell is through designing so that the in fact uniform deposition of zinc on deposition surface to be provided.In addition, some embodiment are designed to provide the zinc deposition with flow, and wherein zinc has non-dendrite morphology intensive, that adhere to.Flow can be used the hybrid element stratification, maybe can use the turbulence element realization mixing to the flow channel interpolation of battery through the turbulent flow under the fair speed or than the turbulent flow under the low velocity.
The 3rd, zinc electrolyte has high concentration, and in certain embodiments, and the concentration of zinc electrolyte is greater than the balance saturated concentration, that is, and and the zinc ion over-saturation of zinc electrolyte.One or more a plurality of improvement in these improvement of different embodiments of the invention combination.
Flow battery group operating current density is the function of the concentration of active ion species.Some embodiments of the present invention provide over-saturation electrolyte, to increase the especially ion concentration between charge period.The zincate electrolyte that can have over-saturation zinc (Zn) ion through chemistry route or the preparation of electrochemistry approach.For example, can prepare zincate electrolyte and have approximate ~ 1 mole to ~ 1.9 moles zinc ion, it is stable above one day that said zincate electrolyte keeps.Referring to Dirkse, Journal of the Electrochemical Society, the 128th volume (No. 7), in July, 1987,1412-1415 page or leaf; Dirkse, Journal ofthe Electrochemical Society, the 134th volume (No. 1), in January, 1987,11-13 page or leaf; And Debiemme-Chouvy&Vedel, Journal of the Electrochemical Society, the 138th volume (No. 9), in September, 1991,2538-2542 page or leaf.It should be noted that to allow to have the zincate particle in the electrolyte that condition is that granularity is less with respect to the size of electrolyte passage (that is the flow channel of battery).In addition, the electrolyte chemical composition that is used for ZnFe flow battery group has the attendant advantages that alkalescence (high pH) electrolyte is provided, and to have more acid substituting electrolyte chemical composition corrosivity littler than many for said alkaline electrolyte chemical composition.Alkali electroless is formed the initial cost and the life-span of the assembly help the flow battery group, said assembly such as, travel to and fro between the plumbing installation and the pump of the cell stacks of flow battery group in order to conveying electrolyte stream.
On the cell deposition surface and the high operating current density through cell stacks reduced the per unit of power cost-effectively or the energy output of battery pack and reduced the integrated operation cost.Embodiments of the invention will provide maintainable higher operating current density through guaranteeing especially during charging (deposition), to avoid or minimize dendrite formation.
Through guaranteeing substantially uniform operating current density on the deposition surface in the battery; And through guarantee in the cell deposition surface or approach to exist all the time fully in the available electrolyte of cell deposition surface, equal ion of even high concentration substantially; To avoid or minimize dendrite formation, wherein ion concentration and high operating current consistent in density and enough or greater than keeping through one or the needed concentration of current density of more a plurality of deposition surfaces.
Under not well-mixed situation; The laminar flow of electrolyte is flowed through, and the high current density operation of battery flow channel causes the deposition surface place or the ion concentration that approaches in the diffusion boundary layer at deposition surface place reduces, and said ion concentration reduces and causes inhomogeneous deposition and dendrite formation.Electrolyte stream fluidised form actuating battery with the mixing (through laminar flow or turbulent flow) in the electrolyte stream of the battery flow channel that causes flowing through; Meeting increases mass tranfer coefficient and reduces the diffusion boundary layer thickness at deposition surface place, and said mass tranfer coefficient increase and diffusion boundary layer thickness reduce and increased the availability of the ion that is used to deposit.Ion (for example; Zinc ion concentration in the ZnFe battery pack in the zincate) high availability allows the higher current density operation; And can not exhaust significantly one or the homogeneous area on more a plurality of cell deposition surface in concentration of electrolyte, and therefore almost do not have or do not have dendrite formation.
The combination that mixes both (both is with respect to prior art batteries) of the increase of electrolyte will reduce or eliminate the formation of dendritic crystal near the zincate ion concentration that increases in the electrolyte and the deposition surface the battery flow channel.To allow the high current density operation of maintainable increase like this and will produce the battery of reduced size, less integral battery door piles up and less whole module, therefore will reduce battery that given power and/or electric current export, pile up and module cost and integrated operation cost.These gained abilities will provide more economical battery pack system and will reduce the energy of battery pack system and the whole cost of power output.
Through designing electrolyte stream and battery flow channel geometry, strengthen battery performance to produce the diffusion boundary layer thickness that enough mixing or turbulence reduce the deposition surface place.
Hereinafter table 1 and table 2 show the high operating current density of the flow in the battery flow channel according to an embodiment of the invention and the average mass tranfer coefficient (k that is associated
m) the illustrative value estimated.Mass tranfer coefficient and the mass transfer rate (mol/cm that passes to electrode surface
2.s) and the concentration difference (mol/cm between bulk solution and the electrode surface place
3) relevant.Also can be according to Sherwood (Sherwood) number or average sherwood number (Sh
m) mixing of the battery flow channel that is used for increasing operating current density is described, said sherwood number or average sherwood number are defined as the zero dimension mass tranfer coefficient, also are defined as the ratio that convection current in the electrolyte transmits the ion that transmits with diffusion.It should be noted that instance based on sherwood number in the correlation calculations hereinafter table of the flow of the 3D turbulence structure of flowing through; Yet, can in spirit of the present invention and category, use other computational methods.i
LBe limiting current density, promptly electrode surface (or electrode solid interface) locate under zero ion concentration with mA/cm
2The current density of meter.i
AppBe favourable battery-operated current density, the purpose of starting from instance in the table 1 is defined as with mA/cm
2Meter i
LApproximate ~ 2/3 times (but those skilled in the art will appreciate that can in other value of use or definition in the spirit of various embodiment of the present invention and the category).V is the mean flow rate in cm/s of electrolyte of battery flow channel of flowing through.C
bBe bulk solution concentration, i.e. the outside active ion concentration of diffusion boundary layer is in mol/l.Hereinafter table 1 and table 2 also provide the illustrative example of these parameters.Although those skilled in the art is familiar with these parameters and term; But additional detail is found in the book, said book such as, " the Advanced Transport Phenomenon:Fluid Mechanics and Convective Transport " of L.Gary Leal; The 9th chapter; Be published in 2007 and " the Unit Operations of Chemical Engineering " of Warren L.McCabe, Julian C.Smith and Peter Harriot the 21st chapter by the Cambridge University Press; Publish (V version, 1993) by McGraw Hill Inc.
| i app(mA/cm 2) | 70 | 100 | 150 | 200 | 250 | 400 |
| C b(mol/L) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
| i L(mA/cm 2) | 105 | 150 | 225 | 300 | 375 | 600 |
| k m(cm/s) | 2.3×10 -3 | 3.1×10 -3 | 4.6×10 -3 | 6.2×10 -3 | 7.8×10 -3 | 12.4×10 -3 |
| Sh m | 64 | 86 | 129 | 172 | 215 | 342 |
Table 1. opereating specification instance, wherein C
b=0.25 (mol/L)
| i app(mA/cm 2) | 70 | 100 | 150 | 200 | 250 | 400 |
| C b(mol/L) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| i L(mA/cm 2) | 105 | 150 | 225 | 300 | 375 | 600 |
| k m(cm/s) | 5.3×10 -4 | 7.7×10 -4 | 1.2×10 -3 | 1.5×10 -3 | 1.9×10 -3 | 3×10 -3 |
| Sh m | 16 | 21 | 32 | 43 | 54 | 86 |
Table 2. opereating specification instance, wherein C
b=1 (mol/L)
For being in 70mA/cm
2To 400mA/cm
2Approximate extents in battery-operated, desirable mass tranfer coefficient is between approximate 5 * 10
-4Cm/s and 1.24 * 10
-2Between the cm/s.For being in 70mA/cm
2To 400mA/cm
2Approximate extents in battery-operated, desirable average sherwood number is between approximate 15 and 350.
The lip-deep zinc deposit thickness of one or more a plurality of cell deposition that shows 8 hours charging operations of following high current density in the table 3 through calculating.
| Current density (mA/cm 2) | 100 | 200 | 400 |
| Thickness of deposits (cm) | 0.17 | 0.34 | 0.68 |
| Deposit capacity (mAh/cm 2) | 800 | 1,600 | 3,200 |
| Sediment quality (g/cm 2) | 0.976 | 1.951 | 3.902 |
The approximate zinc deposit thickness of table 3.8 hour charging
It should be noted that these thickness numerals are proportional linearly with current density and time.For example, for current density 100mA/cm
2, calculate approximate 0.21 millimeter/hour of growth rate; For current density 200mA/cm
2, calculate approximate 0.43 millimeter/hour of growth rate; With for current density 400mA/cm
2, calculate approximate 0.85 millimeter/hour of growth rate.
Although the instance that this paper provides is a ZnFe redox flow batteries group, can use instruction of the present invention and principle to make other redox flow batteries group.For example, can make following battery pack: ZnHBr; ZnBr; CeZn; And ZnCl.
Fig. 2 diagram is according to the sketch map of the flow battery group 200 of some embodiments of the present invention.Fig. 2 is the instance of ZnFe flow battery group.That flow battery group 200 has is anodal 212, negative pole 222 and film 210, exists zinc-plated regionally 224 on the surface of negative pole 222, and film 210 is separated anodal passage 211 and negative pole passage 221.To anodal electrolysis liquid pipeline and negative pole electrolysis liquid pipeline, indicate the electrolyte stream of divider passages in the battery of flowing through and the electrolyte stream of all the other fluid circuits of flowing through respectively with arrow 213 and arrow 223.Each fluid circuit comprises cell channel (211 and 221), the tranquil characteristic 262 of optional flow (such as, the tranquil characteristic of the flow shown in Figure 14), electrolyte accumulator tank
(240 and 250; Electrolyte accumulator tank 240 contains anodal electrolyte sodium ferrocyanide/ferricyanic acid sodium solution in this instance, electrolyte accumulator tank 250 contains negative pole electrolyte sodium zincate solution in this case), pump 263 and one or more a plurality of flow sensor 264.Pump 263, transducer 264 and pump controller 265 comprise the fluidised form in the control battery through being configured to control the electrolyte flow through battery, that is, fluidised form can be and runs through laminar flow, mixed flow and/or the turbulent flow that the application's case is described.
Speed through counting cell channel volume, electrolyte stream and be desirably in the amount that the zincate at battery outlet port chamber place exhausts; The amount of the electrolyte of confirming pump through each side of electrochemical cell has wherein been considered energy storage duration and the conduit volume and the duct section length that define electrolyte holding tank size.To the electrolyte of every cell stacks specified rate, depend on the character of the electrolyte that is used for electrochemical cell, use under highly basic (for example, 2 to 5N NaOH) or strong acid condition, has durability and long-life building material is selected the pump size.Usually, each cell stacks is selected two pumps, the corresponding pump of each electrolyte.The cardinal principle acceptable material of structure comprises polypropylene, polyethylene, fluorinated polymer, polyether-ketone, polysulfones, polyphenylene sulfide etc.Various transducers are through selecting to measure fluid velocity, mobile direction, temperature, pressure and other tolerance of fluid in the entrance of holding tank, pipeline, pump, cell channel and each position in the exit point.Each data-signal from each transducer transfers to data control system through holding wire or through Wireless Transmitter.The data control system record data stream also uses algorithm, set point and control input; Data-signal is sent to fan (being used for cooling when needed), valve and engine; (for example to control according to order; Increase, reduce or keep) engine speed and valve position, and then increase, reduce, keep constant or the change flow direction.Data control system can be sent to alarm signal and other performance data the control room of remote location under certain conditions.The pipeline of travelling to and fro between cell channel through design and through design size minimizing the branch current loss, and depend on the character of electrolyte, select the material of constructing to the durability under highly basic or strong acid condition.Electro-chemical systems is positioned at the fluid containment internal system substantially, and said fluid containment system comprises appropriate sensor and siren, to indicate any electrolyte leakage.
Fig. 3 illustrates the perspective schematic view of battery 300.For example, battery 300 can be that roughly 0.5cm is thick, wherein large-size for 30cm * 30cm roughly to up to 132cm * 67cm.The cross-sectional view of illustrated section X-X in Fig. 7.Fig. 3 is shown in the battery 300 that both sides have the dipolar configuration element.Battery has anodal passage 211 and negative pole passage 221, and anodal passage 211 is separated through film 230 with negative pole passage 221.Pump negative pole electrolyte through the negative pole passage, and pump anodal electrolyte through anodal passage, as shown in the figure; Show anodal electrolyte flow stream and negative pole electrolyte flow stream through arrow 213 and arrow 223 respectively.The further details of battery is provided above with reference to Fig. 7.
The battery 300 of Fig. 3 in Fig. 4 illustrated frame 410.Battery 300 is centered on by framework 410; Framework 410 is used for film (barrier film) and dipolar configuration element are fixed on the appropriate location; Thereby produce flow channel, seal flow passage the edge, the position of attached electrolyte stream and return pipe is provided, and battery 300 can contain electrolyte distribution manifold and flow calmness characteristic alternatively.The anodal electrolyte stream of the turnover framework that provides to battery 300 and negative pole electrolyte stream are indicated through arrow 213 and arrow 223 respectively.
More detailed instance according to the battery of some embodiments of the present invention is provided in Fig. 5 to Fig. 7.For example, the large scale of battery can be 30cm * 30cm, 90cm * 90cm, 60cm * 90cm, 45cm * 90cm or 132cm * 67cm.The instance of cross sectional dimensions of the assembly of battery is provided in Fig. 5 to Fig. 7.Yet, the invention is not restricted to these battery sizes, and the present invention can be used for littler or larger sized battery.With the cross-sectional illustration battery, and the cross section is perpendicular to the big surface of battery.(for example, referring to the cross section X-X among Fig. 3.) power density is that battery chemistries is formed and the function of battery current density.For example, for 200mA/cm
2Under ZnFe, discharge energy density is about 0.3W/cm
2For the battery size that preceding text are listed, every battery gained power will be respectively approximate 274W, 2.43kW, 1.60kW, 1.22kW and 2.45kW.
Fig. 5 illustrates first instance of the schematic cross-section of bipolar ZnFe redox flow batteries Battery pack of the present invention.Diagram single battery Battery pack, said single battery Battery pack comprise negative half-cell 220, positive half-cell 210 and dipolar configuration element 270.The positive half-cell of dipolar configuration element 270 separating adjacent batteries and negative half-cell.(referring to Fig. 6.) dipolar configuration element 270 in this instance is 50% graphite fibre/PPS connectors, on said connectors, has cadmium metal clockwork spring (strike) 271.(PPS is a polyphenylene sulfide.Can use other polymeric material with conductive filler combination to replace the PPS in the structure of dipolar configuration element; Said other polymeric material such as; Polyether-ketone, polysulfones, polyethylene, polypropylene etc.; Said conductive filler such as, graphite fibre or thin slice, some carbon dust and carbon black, CNT, conductive metal powder etc.) positive half-cell 210 comprises porous Ni mesh oxidation-reduction electrode, the anodal passage 211 of said porous Ni mesh oxidation-reduction electrode complete filling, that is, anodal electrolyte stream is through porous Ni mesh oxidation-reduction electrode.Negative half-cell 220 comprises the plating Zn zone 224 and negative pole electrolyte flow passage 221 of the variable thickness on the Cd metal clockwork spring 271.The positive half-cell of battery passes through film 230 with separate with negative half-cell separately, and film 230 is processed by material or another kind of diaphragm material such as Nafion-114.Film 230 keeps zincate and electrolytic iron matter to separate, but Na ion and water can move through film.Membrane material can be the diaphragm material that has or do not have grafting ion chemistry species.
For with high current density (for example, density of charging current 200mA/cm
2) bipolar cell of application drawing 5, in the negative pole flow region, produce higher mass transfer rate.Can realize this result through more than the mixing rate that mixing rate is increased to the prior art battery and/or through the electrolyte flow flow rate is increased to more than the electrolyte flow flow rate of prior art battery.Can carry out this operation through not reaching the turbulent flow attitude to cell channel interpolation hybrid element or through gathering way or introducing the turbulence producing component that hereinafter is discussed through gathering way till realizing turbulent flow or passing through.It should be noted that the zinc depositing current density is the function of fluid (electrolyte) speed and Reynolds number." The Effect of Electrolyte Flow on the Morphology of Zinc Electrodeposited from Aqueous Alkaline Solution Containing Zincate Ions " referring to R.D.Naybour; J.Eletrochem.Soc.; The 520-525 page or leaf, in April, 1969.It should be noted that the electroless copper deposition operation current density also is the function of the concentration of active specy.
Fig. 6 illustrates second instance of the schematic cross-section of bipolar ZnFe redox flow batteries Battery pack.Anodal 612 comprise porous Ni mesh oxidation-reduction electrode, and said porous Ni mesh oxidation-reduction electrode is attached to bipolar Ni/Cu electrode 272, that is, the Ni mesh is attached to the Ni face of bipolar electrode.Anodal electrolyte flow zone is occupied by porous Ni mesh.Negative pole 622 can comprise high surf zone Cu or the Ni mesh that applies Cd, Sn or Pb, and the porosity of said high surf zone Cu or Ni mesh is (for example) 60% to 98%.Cu that is coated or Ni mesh are attached to the Cu face of bipolar electrode 272.Cu that is coated or Ni mesh occupy negative pole electrolyte flow zone, and the mixing in the mesh generation negative pole electrolyte stream, and do not need higher fluid velocities.Battery is arranged so that the Cu or the Ni mesh electrodepositable that are coated have the Zn up to approximate 20% to 70% volume.Fig. 6 also illustrates bipolar electrode 272 (or dipolar configuration element 270 of Fig. 5) how separate batteries and adjacent cell and help the efficient and cost-efficient structure of cell stacks.In Fig. 6, illustrate adjacent cell.
Fig. 7 illustrates the 3rd instance of the schematic cross-section of bipolar ZnFe redox flow batteries Battery pack.(Fig. 7 is the cross section X-X among Fig. 3.) anodal passage 211 comprises porous Ni mesh oxidation-reduction electrode, said porous Ni mesh oxidation-reduction electrode is attached to bipolar Ni/Cu electrode 272, that is and, the Ni mesh is attached to the Ni face of bipolar electrode.Anodal electrolyte flow zone is occupied by porous Ni mesh.Negative pole passage 221 comprises zinc metal plating zone 224 and characteristic 280, mixing or the turbulence of characteristic 280 through being configured to inducement efficient.The instance graph of characteristic 280 is shown among Fig. 8 to Figure 13 and describes hereinafter.(should note; Characteristic 280 can be positioned in the flow channel of deposition surface top; As shown in Figure 7, or in other embodiments, characteristic 280 can directly be positioned on the deposition surface; Shown in Figure 11 to Figure 13, and Fig. 8 to Figure 10 diagram can be positioned on the deposition surface or the structure of deposition surface top.) to produce the two-forty mixing of flow, the while not necessarily needs high-speed (therefore can cause the higher power dissipation of pumping) to these characteristics through design.With the Zn metal plating on the Cu of bipolar electrode 272 face.The Cu face possibly also be coated with Cd, Sn or Pb in substituting ground.It should be noted that the cylinder shown in Figure 11 to Figure 13, cone and pyramid will be processed and be illustrated as and have sharp-pointed edge and point by non-conducting material.Yet if hope to process cylinder, cone and pyramid by electric conducting material, so said cylinder, cone and pyramid should have more blunt edge and terminal but not sharp-pointed edge and point.(should note; In order to improve the uniformity that Zn electroplates; If in order to induce mix and/or turbulence be characterized as conduction; Then said characteristic should not have sharp-pointed point or edge, and sharp-pointed point and edge are the electric field concentrator and cause unfavorable inhomogeneous plating and even cause dendritic crystal to form.) in addition, characteristic should not occupy excessive bulk and make the flow through flow of anode passages receive unsuitable obstruction---vide infra to obtain further details.
It should be noted that to be directed against the special modality geometry, define the condition of inducing turbulent flow easily through using (for example) Reynolds number.Those skilled in the art are afamiliar with the calculating of Reynolds number, comprise calculating to the Reynolds number of the passage that contains characteristic (such as, those characteristics shown in Fig. 8 to Figure 13).Haply, for the battery of rectangular channel in fact that has shown in Fig. 7, approximate at least greater than 1,300 or be preferably 2,000 Reynolds number and can wherein define characteristic length in order to guarantee turbulent flow through hydraulic diameter.The hydraulic diameter of narrower flow channel (L>> W) is the twice of channel thickness, i.e. 2W, and wherein L and W are the length and the width of the flow channel measured perpendicular to fluid flow direction.(referring to Fig. 3.）
For the battery that comprises characteristic shown in Fig. 8 to Figure 13 shown in Fig. 7, but the lower efficient mixing of Reynolds number sufficient to guarantee or two-forty mix, for example, but at least approximate 8 or the bigger efficient mixing of Reynolds number sufficient to guarantee.Yet specific Reynolds number will change with battery and flow channel design and composite character.
Fig. 8 diagram is suitable on flow battery group electrode surface, inducing the instance of the structure of mixing or turbulence in the electrolyte stream.The litzendraht wire mesh 820 of away minor segment is illustrated as on the part on electrode 810 surfaces.The electrolyte flow direction is indicated through arrow; Flow and be in substantially parallel relationship to the surface of electrode 810.Gauze hole 820 is interrupted fluid and is flowed, thereby on electrode surface, induces the required mixing in laminar flow, half turbulent flow or the turbulent flow.It should be noted that also can be through making mesh approach the surface of electrode 810 and not necessarily on the surface of electrode 810, realize similar effect.The linear diameter that is fit to will between channel thickness 20% and 50% between.
In certain embodiments, the gauze hole is part conduction and that serve as electrode surface, thereby increases total electrode surface areas (except that the mesh that serves as hybrid element).In other embodiments, mesh is non-conductive and on smooth electrode surface, mixes flow.When non-conductive mesh was clipped between electrode and the film, non-conductive mesh also can be in order to the electrode of guaranteeing appointment and intermembranous separated.In other embodiments, possibly have the several layers mesh, some are what conduct electricity, and some are non-conductive.In this type instance, conductive mesh is adjacent to electrode, and non-conductive mesh is between conductive mesh and film.Non-conductive mesh serves as sept keeping plate surface away from film, and serves as the flow mixed structure.Non-conductive mesh can be processed by plastics or other non-conducting material or material of low conductivity.In further embodiment, possibly there are a series of adjoining cells of conductivity with variation.This structure will be confirmed internal field, and said internal field control local current distributes, and therefore controls electroplating evenness.
Fig. 9 diagram is suitable for inducing another structure of the mixing in laminar flow electrolyte stream or the turbulent flow electrolyte stream.The non-litzendraht wire mesh 830 of away minor segment is illustrated as on the part on electrode 810 surfaces.The electrolyte flow direction is indicated through arrow; Flow and be in substantially parallel relationship to the surface of electrode 810.Gauze hole 830 is interrupted fluid and is flowed, thereby on electrode surface, induces the required mixing in laminar flow or the turbulent flow.It should be noted that also can be through making mesh approach the surface of electrode 810 and not necessarily on the surface of electrode 810, realize similar effect.The linear diameter that is fit to will between channel thickness 10% and 50% between.In certain embodiments, can on cell channel, pile up or at interval a plurality of lines are set, further to strengthen the property.
Figure 10 diagram is suitable for inducing the another structure of the mixing in laminar flow electrolyte stream or the turbulent flow electrolyte stream.Parallel lines/pipe 840 is illustrated as on the part on electrode 810 surfaces.The electrolyte flow direction is indicated through arrow; The flow surface be in substantially parallel relationship to electrode 810 and perpendicular to the major axis of line/pipe.Line/pipe 840 interrupts fluid and flows, thereby on electrode surface, induces desirable turbulent flow (non-laminar flow).It should be noted that also can be through making line/pipe approach the surface of electrode 810 and not necessarily on the surface of electrode 810, realize similar effect.The linear diameter that is fit to will between channel thickness 10% and 90% between.
Figure 11 diagram is used for inducing the part of character array of the mixing of laminar flow electrolyte stream or turbulent flow electrolyte stream.Array of cylinders 850 is illustrated as on the part on electrode 810 surfaces.The electrolyte flow direction is indicated through arrow; Flow and be in substantially parallel relationship to the surface of electrode 810.Array of cylinders 850 is interrupted fluid and is flowed, thus the required mixing on electrode surface in the induced flow.Illustrated cylinder is formed by non-conducting material and can have sharp-pointed edge.The cylinder height that is fit between channel thickness 20% and 100% between.Interval and diameter must reach the degree that produces the turbulence under the expectation flow rate.
Figure 12 diagram is used for inducing the part of another feature array of the mixing of laminar flow electrolyte stream or turbulent flow electrolyte stream.Cone (or tapered cylinder) array 860 is illustrated as on the part on electrode 810 surfaces.The electrolyte flow direction is indicated through arrow; Flow and be in substantially parallel relationship to the surface of electrode 810.Cone array 860 interrupts fluid and flows, thereby on electrode surface, induces the ideal in laminar flow or the turbulent flow to mix.Illustrated tapered cylinder is formed by non-conducting material and can have sharp-pointed point.The cylinder height that is fit between channel thickness 20% and 100% between.At interval must reach to produce and mix, reducing of channel thickness when the while can not increase along with the Zn thickness of deposits and increase the degree of flow resistance inadequately with diameter.
Figure 13 diagram is used for inducing the part of another character array of the mixing of electrolyte stream.This is in order to explain that the shape except that cylinder also is fit to.Pyramid array 870 is illustrated as on the part on electrode 810 surfaces.The electrolyte flow direction is indicated through arrow; Flow and be in substantially parallel relationship to the surface of electrode 810.Pyramid array 870 interrupts fluid and flows, thus the required mixing of induced flow on electrode surface.Illustrated tapered feature is formed by non-conducting material and can have sharp-pointed edge, and illustrated tapered feature can have other cross section, and is for example, leg-of-mutton, other is polygonal or oval-shaped cross section.The feature height that is fit between channel thickness 20% and 100% between.Interval and diameter must reach the degree that produces the mixing under the expectation flow rate.Taper can be through selecting keeping the mixing of two-forty, reducing of channel thickness in the time of can not increasing along with the Zn thickness of deposits simultaneously and increase flow resistance inadequately.
Fig. 8 to Figure 13 provides can be in order to the scope of the instance of on electrode surface, inducing the characteristic of mixing in the electrolyte stream.Yet these instances are not intended for comprehensive inventory, and those skilled in the art will understand more after reading this disclosure and be suitable for inducing the further characteristic of mixing in laminar flow and/or the turbulent flow.For example, further characteristic can comprise: above-described combination of features; Conductive mesh and non-conductive mesh; Band; Foaming structure; Other layout with line or pipe.
Array of figure shown in Figure 11 to Figure 13 is shown the regular array of characteristic; Yet these arrays also can have the randomly located characteristic of randomly located characteristic or part.
The characteristic pattern of Fig. 8 to Figure 13 is shown on the surface of flow battery group electrode.Yet, this category feature can be just before electrolyte flows on entire electrode substituting ground or additionally be arranged in electrolyte stream; Said characteristic can attached (for example) to the inner surface that electrolyte is delivered to the plumbing installation in the half-cell.
In the operation of commercial liquid galvanic battery group, the power that the system of pumping consumes is the key factor of the overall production of optimization battery pack system.Although higher fluid is pumped speed and induced higher mixability in the battery, higher fluid is pumped speed also needs more power of pumping more, said more power power and energy that battery pack system carries that finally detract of pumping more.The higher speed of pumping also causes higher wear, therefore causes more frequent preventive maintenance.In the battery pack design, can weigh and consider pump power, mixing and turbulence.The laminar flow of travelling to and fro between battery at inside battery and outside and flowing pipe reduces substantially pumps power requirement.When being used for turbulence operation at the flow channel mixed electrolytic solution of battery; Can (for example) than the low velocity zone turbulence be die-offed through permission; Said than the low velocity zone in, (for example) used and to be reduced flow velocity and to recover laminar flow such as the structure that is illustrated among Figure 14.Guarantee battery any have a mind to the outside flow of turbulent region be laminar flow or in fact laminar flow reduced pump power consumption.
Figure 14 illustrates the cross section of modified pipe in the exit of half-cell, and said pipe makes when moving through the plumbing installation remainder at electrolyte turbulent flow tranquil and laminar flow is provided through design.The electrolyte that turbulence is flowed is in half-cell flows to first section 1410 of pipe.Electrolyte gets into second section 1420 of pipe subsequently, and in second section 1420 of pipe, the cross section of pipe increases.Along with pipe 1420 cross sections increase, the speed of electrolyte reduces, and turbulent flow is tranquil, thereby produces laminar flow.The electrolyte of Laminar Flow gets into the 3rd section 1430 of pipe subsequently, and in the 3rd section 1430 of pipe, the cross section of pipe reduces, so that the electrolyte after the calmness is delivered in the plumbing installation 1440 through funnel, and plumbing installation 1440 continuity electrolyte pipelines.The direction of electrolyte flow is indicated through arrow.
The electrolyte stream that can make the battery flow channel of flowing through is oppositely with the uniformity of improving mixing, deposition and the electrolyte of avoiding exhausting the deposition surface place.
Support can be in order to mesh (or screen cloth) hybrid element in the moving passage of supporting stream, to avoid said mesh contact membranes or electrode and to avoid mesh substantially because high flow rate, turbulence or variations in temperature and bending or flexing.
Those skilled in the art should know the many definition and the tolerance of turbulence.Turbulence in this situation means that substantially (speed is vector for the variation of flow velocity; And change and comprise the variation of speed and the variation of flow direction); The variation of said flow velocity comprises the mixing that causes electrolyte stream, with avoid deposition exhaust during (charging) or interdischarge interval remove the deposition surface place or approach the deposition surface place through depositing ion.
When the definition of uniform deposition means between charge period deposition in fact on the deposition surface of battery between charge period, do not form or less formation dendritic crystal.Those skilled in the art will appreciate that on the deposition surface with battery on some variations of (maybe less than 20%) deposit thickness be intrinsic, especially the time with high current density with the ion manipulation of electrolyte middle and high concentration.
The mixing of two-forty means the mixing in laminar flow or the turbulent flow substantially, exhausts with the plating ion of avoiding or minimize especially at the deposition surface place or approach the deposition surface place.Can realize being used for the two-forty mixing of various embodiment as follows: (1) is with passage and the mixing arrangement that departs from deposition surface; (2) with the mixing arrangement on passage and the deposition surface; (3) with mixing arrangement on passage and the deposition surface and the mixing arrangement that departs from deposition surface; Or (4) are with passage, mixing arrangement and higher electrolyte speed.
First; The distance that is positioned at the distance electrode deposition surface at hybrid element or device is the approximate at least twice place of diffusion boundary layer thickness; And the cross-sectional area of hybrid element or device is approximate 10% to 80% of a cell channel cross-sectional area; From approximate 25% to 60% o'clock, can realize the mixing of two-forty ideally; Or the distance that is positioned at the distance electrode deposition surface at mixing arrangement is approximate at least 125 microns places, and the cross-sectional area of mixing arrangement is the approximate 10% to 80% of cell channel cross-sectional area, is preferably at approximate 25% to 60% o'clock, can realize the mixing of two-forty; Or be the approximate at least twice place of diffusion boundary layer thickness in the distance that hybrid element or device are positioned at the distance electrode deposition surface; And the cross-sectional area of hybrid element or device is approximate 10% to 80% of a cell channel cross-sectional area; Be preferably approximate 25% to 60%; Wherein mixing arrangement can be realized the mixing of two-forty on the cell channel width and when cell channel length has repeated characteristic (or approximate repeated characteristic); Or be the approximate at least twice place of diffusion boundary layer thickness in the distance that hybrid element or device are positioned at the distance electrode deposition surface; And the cross-sectional area of hybrid element or device is approximate 10% to 80% of a cell channel cross-sectional area; Be preferably approximate 25% to 60%; Wherein mixing arrangement has repeated characteristic (or approximate repeated characteristic) on the cell channel width and along cell channel length; And along the spacing of the repeated characteristic of cell channel length is at least approximate 1.1 times time of spacing of the repeated characteristic on the channel width, can realize the mixing of two-forty.
Second; One or more a plurality of hybrid element or device be attached to the electro-deposition surface; And the ratio of mixing arrangement leading edge repeat distance is approximate at least five times of mixing arrangement height of distance electrode deposition surface; And the optional group below self-contained of the shape of mixing arrangement: when line, mesh, screen cloth, hemisphere, circle, semicircle or rectangular shape or other shape or above-mentioned combination, can realize the mixing of two-forty.
The 3rd; One or more a plurality of hybrid element or device be attached to the electro-deposition surface; In conjunction with on be positioned at the distance electrode deposition surface distance be second mixing arrangement at the approximate at least twice place of diffusion boundary layer thickness; And the cross-sectional area of second mixing arrangement is the approximate 10% to 80% of cell channel cross-sectional area, is preferably at approximate 25% to 60% o'clock, can realize the mixing of good speed.
The 4th; The distance that is positioned at the distance electrode deposition surface at hybrid element or device is the approximate at least twice place of diffusion boundary layer thickness, and the cross-sectional area of hybrid element or device is the approximate 10% to 80% of cell channel cross-sectional area, is preferably approximate 25% to 60%; And electrolyte flow speed is approximate at least 5cm/s; Be preferably at least approximate 25cm/s, and during more preferably approximate at least 50cm/s, can realize the mixing of two-forty.
In some applications, flow battery group (such as, some embodiments of the present invention) can be used for frequency adjustment.In addition, some embodiments of the present invention can be used for other shorter duration power needs (such as, UPS (can not interrupt power system)) or shorter responding power subsequent use.Need for shorter duration power, some embodiment of flow battery group of the present invention can the higher density of charging current and discharge current density (such as, greater than 200mA/cm roughly
2) operation down.
In other embodiments, the flow battery group can comprise one or more persons in following: the Reynolds number of flow channel is approximate greater than 1300; The sherwood number of flow channel is approximate greater than 21; Uniform Gao Dianliumidu>100mA/cm
2In flow channel, there is at least one hybrid element; In flow channel, exist at least one turbulence to induce element; Mass tranfer coefficient is approximate greater than 7.7 * 10
-4M/s; Be at least 5 minutes duration or be the duration of at least one hour with charge cycle.
In certain embodiments, high-performance flow battery group can comprise cell stacks, said cell stacks Zai>100mA/cm
2Charge cycle during have maintainable operating current density in the cell area in cell stacks.In certain embodiments, high performance flow battery group based on zinc can comprise with on the deposition surface in the battery that zinc is deposited on battery pack greater than the speed of 0.1mm per hour, and in other embodiments, and deposition rate is greater than 0.2mm per hour.In addition; In certain embodiments; Can comprise for the method for high-performance ZnFe flow battery group charging: zinc is grown in or zinc is deposited on the deposition surface of battery in the battery pack greater than the speed of 0.1mm per hour; And in other embodiments, growth or deposition rate are greater than 0.2mm per hour or greater than 0.4mm per hour.
In another embodiment; High-performance redox flow batteries group comprises at least one battery; Said at least one battery comprise low resistance at least one positive half-cell anodal with at least one negative half-cell in the low resistance negative pole; Wherein the resistance of the resistance of low resistance positive pole and low resistance negative pole is enough little; With the even high current density on the zone of the deposition surface that obtains at least one battery; With the electrolyte stream of two-forty mixed flow through the flow channel of at least one half-cell, wherein electrolyte has sufficiently high active ion species concentration near the deposition region of deposition surface, during obtaining to maintain charge cycle on the deposition surface, to pass through the deposition rate of the even high current density of deposition surface; Mass tranfer coefficient near the flow of deposition surface is enough to keep the enough concentration of electrolytes near deposition surface at least, with the uniform deposition in fact in the zone that obtains deposition surface.
In another embodiment, comprise for the method for high-performance flow battery group charging: under than the higher voltage of the voltage of flow battery group, enough supply of electrical energy to be delivered to the flow battery group; On the anodal and low resistance negative pole even high current density is provided in low resistance, said high current density passes the zone of deposition surface of at least one half-cell of flow battery group; The flow through electrolyte stream of flow channel of at least one half-cell of generation; Said electrolyte stream is mixed with two-forty near the deposition region of deposition surface; Wherein electrolyte has sufficiently high active ion species concentration, to obtain to maintain the deposition rate of passing through the even high current density of deposition surface between charge period on the deposition surface; Keep near the mass tranfer coefficient of the flow of deposition surface enough greatly, keeping enough concentration of electrolytes, thereby obtain the uniform deposition in fact in the zone of deposition surface near deposition surface.Flow can be laminar flow or turbulent flow.The mixing of two-forty is in is enough to keep mass tranfer coefficient greater than 7.7 * 10
-4In the scope of cm/s.
In addition; The present invention includes the method for optimization high-performance redox flow batteries group; Said method comprises: the flow rate and the flow channel of design flow battery group; Said flow rate and flow channel through optimization to guarantee to satisfy one in the following parameter or more persons: under best fluid velocity, even mass transfer rate is arranged on the deposition surface; Local current densities is approximate less than 2/3xi
L, but enough high to prevent mossy deposition (local current densities of the non-dendrite morphology that in other words, is suitable for providing intensive, adhere to); Exhaust being similar to concentration for entrance concentration along flow channel (on the Zn side)<10%.
Experiment confirm: the solubility of (1) zinc in 4N NaOH be 0.73M with (2) at 40 ℃, under the rotary speed 120rpm, the limiting current density of this solution (at the rotating disk electrode (r.d.e) place) is 121mA/cm
2
Over-saturation zinc electrolyte, i.e. 0.73M Zn among the 4N NaOH
++Preparation as follows.Step 1:, prepare stoste (1M Zn among the 5.5N NaOH through 8.139g ZnO (m.w 81.39g/mol) is prepared to 100ml under constant agitation with 30gmNaOH spherolite (m.w.40g/mol) combination and with D.I water
++).Gained solution is 1M Zn
+++ 5.5N NaOH.Step 2: through taking 100ml (1M Zn among the 5.5N NaOH
++) stoste and said stoste being prepared to 137.5ml with D.I water, with (1M Zn
++/ 5.5NNaOH) being diluted to 4N NaOH solution, gained solution is the 0.73M Zn among the 4N NaOH
++(it should be noted that Zn among the 4N NaOH that is reported
++Solubility limit is 0.37M.) should note; Find that the electrolyte that NaOH concentration is in the 2N-4N scope provides gratifying zincate ion concentration, the combination of acceptable ferrous ion concentration and acceptable solution corrosion property, and the NaOH concentration that is higher than 4N causes ferrous ion concentration to reduce rapidly and produces more acrid electrolyte.
Experiment confirm, 0.73M Zn among the 4N NaOH
++With 0.4M Zn among the 2.2N NaOH
++Stable reach at least around.
Although with reference to the specific description the present invention of some embodiment of the present invention, one of ordinary skill in the art should be easily clearer, can under the situation that does not break away from spirit of the present invention and category, carry out the change and the modification of form and details.
Claims (15)
1. flow battery group, said flow battery group comprises:
At least one battery, said at least one battery comprise the low resistance negative pole in anodal with the negative half-cell of low resistance in the positive half-cell; With
Pump, said pump are used to make circulate electrolyte to pass through the flow channel of said negative half-cell, and wherein said pump and said passage are through being configured to provide said electrolyte mixing near the two-forty in the deposition region of deposition surface;
The concentration of metal ions of wherein said electrolyte is greater than the balance saturated concentration of metal ion in the said electrolyte.
2. flow battery group as claimed in claim 1; The mass tranfer coefficient of the said electrolyte in the wherein said deposition region is enough to keep the concentration of electrolyte near the metal ion of said deposition surface, to obtain the in fact uniform deposition of metal on said deposition surface.
3. flow battery group as claimed in claim 1, wherein said electrolyte has sufficiently high concentration of metal ions, with the deposition rate of the said even high current density during obtaining to keep charge cycle on the said deposition surface.
4. flow battery group as claimed in claim 1, the solubility of the zinc of wherein said electrolyte in 4N NaOH is greater than 0.37M.
5. flow battery group as claimed in claim 1, the said electrolyte flow of the said flow channel of wherein flowing through is a turbulent flow.
6. flow battery group as claimed in claim 1, the sherwood number of wherein said flow channel is approximate greater than 21.
7. flow battery group as claimed in claim 1, said flow battery group further comprise at least one hybrid element in said flow channel.
8. flow battery group as claimed in claim 7, wherein said hybrid element is selected from the group that is made up of following: line, cone array, pyramid array, foam, mesh and pipe.
9. flow battery group as claimed in claim 1, said flow battery group further comprise the tranquil structure of flow, and the tranquil structure of said flow is positioned in the said electrolyte pipeline after the said flow channel of said negative half-cell.
10. flow battery group as claimed in claim 1, wherein said flow battery group are ZnFe flow battery group.
11. method to the charging of flow battery group; Said method comprises: make the flow channel of circulate electrolyte through half-cell negative in the said flow battery group, wherein said flow channel is mixing near the two-forty in the Metal Deposition zone of the deposition surface of said negative half-cell through being configured to provide said electrolyte.
12. method as claimed in claim 11, the concentration of metal ions of wherein said electrolyte is greater than the balance saturated concentration of metal ion described in the said electrolyte.
13. method as claimed in claim 11; Said method further comprises: the low resistance of said flow battery group anodal with the low resistance negative pole on uniform high current density is provided, said high current density passes through near the said Metal Deposition of the said deposition surface of said negative half-cell regional.
14. a ZnFe flow battery group, said ZnFe flow battery group comprises:
At least one battery, said at least one battery comprise the low resistance negative pole in anodal with the negative half-cell of low resistance in the positive half-cell;
Pump, said pump are used to make circulate electrolyte to pass through the flow channel of said negative half-cell, and wherein said pump and said passage are through being configured to provide said electrolyte mixing near the two-forty in the deposition region of deposition surface;
The zinc metal ion concentration of wherein said electrolyte is greater than the balance saturated concentration of zinc metal ion described in the said electrolyte; And the mass tranfer coefficient of the said electrolyte in the wherein said deposition region is enough to keep the concentration of electrolyte near the zinc metal ion of said deposition surface, to obtain zinc metal uniform deposition in fact on said deposition surface under uniform high current density.
15. like claim 1 or 14 described flow battery groups, wherein said uniform high current density is greater than 70mA/cm
2
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| US61/319,248 | 2010-03-30 | ||
| US32278010P | 2010-04-09 | 2010-04-09 | |
| US61/322,780 | 2010-04-09 | ||
| PCT/US2011/030613 WO2011126908A2 (en) | 2010-03-30 | 2011-03-30 | High performance flow battery |
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|---|---|---|---|
| CN201610341416.9A Expired - Fee Related CN106159189B (en) | 2010-03-30 | 2011-03-30 | High-performance ZnFe flow battery group |
Country Status (4)
| Country | Link |
|---|---|
| US (4) | US20110244277A1 (en) |
| EP (1) | EP2553752A2 (en) |
| CN (2) | CN102823046B (en) |
| WO (1) | WO2011126908A2 (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039729A (en) * | 1974-05-09 | 1977-08-02 | Deutsche Automobilgesellschaft Mbh, Firma | Rechargeable galvanic cell with zinc electrode and auxiliary structure |
| US4180623A (en) * | 1977-12-19 | 1979-12-25 | Lockheed Missiles & Space Company, Inc. | Electrically rechargeable battery |
| US5439757A (en) * | 1992-10-14 | 1995-08-08 | National Power Plc | Electrochemical energy storage and/or power delivery cell with pH control |
| CN101677136A (en) * | 2008-09-18 | 2010-03-24 | 中国人民解放军63971部队 | Electrolyte solution for alkaline zinc flow battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923550A (en) * | 1970-10-09 | 1975-12-02 | Aga Ab | Method and apparatus for avoiding dendrite formation when charging accumulator batteries |
| US3907603A (en) * | 1973-01-29 | 1975-09-23 | Meer Danilovich Kocherginsky | Storage cell with dissoluble negative line electrodes |
| EP0190078A3 (en) * | 1985-01-30 | 1987-04-08 | S.E.R.E.G.I.E. | Charging method for an electrochemical generator with a negative zinc electrode, and generator for using said method |
| WO1999039397A1 (en) * | 1998-01-28 | 1999-08-05 | Chemieco S.R.L. | Redox flow battery system and cell stack |
| US20100196768A1 (en) * | 2007-04-27 | 2010-08-05 | Gregory Roberts | Electrolyte management in zinc/air systems |
| WO2011103142A1 (en) * | 2010-02-16 | 2011-08-25 | Fluidic, Inc. | Electrochemical cell, and particularly a cell with electro deposited |
| EP2553752A2 (en) * | 2010-03-30 | 2013-02-06 | Applied Materials, Inc. | High performance flow battery |
-
2011
- 2011-03-30 EP EP11766512A patent/EP2553752A2/en not_active Withdrawn
- 2011-03-30 CN CN201180016873.6A patent/CN102823046B/en not_active Expired - Fee Related
- 2011-03-30 CN CN201610341416.9A patent/CN106159189B/en not_active Expired - Fee Related
- 2011-03-30 WO PCT/US2011/030613 patent/WO2011126908A2/en active Application Filing
- 2011-03-30 US US13/076,337 patent/US20110244277A1/en not_active Abandoned
-
2012
- 2012-10-05 US US13/646,189 patent/US20130029187A1/en not_active Abandoned
-
2014
- 2014-08-27 US US14/470,779 patent/US10008729B2/en not_active Expired - Fee Related
-
2018
- 2018-05-30 US US15/992,332 patent/US20180277864A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039729A (en) * | 1974-05-09 | 1977-08-02 | Deutsche Automobilgesellschaft Mbh, Firma | Rechargeable galvanic cell with zinc electrode and auxiliary structure |
| US4180623A (en) * | 1977-12-19 | 1979-12-25 | Lockheed Missiles & Space Company, Inc. | Electrically rechargeable battery |
| US5439757A (en) * | 1992-10-14 | 1995-08-08 | National Power Plc | Electrochemical energy storage and/or power delivery cell with pH control |
| CN101677136A (en) * | 2008-09-18 | 2010-03-24 | 中国人民解放军63971部队 | Electrolyte solution for alkaline zinc flow battery |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105122527A (en) * | 2013-03-04 | 2015-12-02 | 云储能有限公司 | Rechargeable copper-zinc cell |
| CN105122527B (en) * | 2013-03-04 | 2018-05-22 | 云储能有限公司 | Rechargeable electrolytic copper-zinc battery |
| CN104716374A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| CN104716374B (en) * | 2013-12-15 | 2017-04-12 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| CN110429302A (en) * | 2014-02-27 | 2019-11-08 | 维智能源系统公司 | With shunt current to the flow cell of electrode |
| CN106654314A (en) * | 2016-11-04 | 2017-05-10 | 大连融科储能技术发展有限公司 | Electrolyte storage tank and flow cell |
| CN106654314B (en) * | 2016-11-04 | 2019-05-24 | 大连融科储能技术发展有限公司 | Electrolyte storage tank and flow battery |
| WO2018103517A1 (en) * | 2016-12-10 | 2018-06-14 | 中国科学院大连化学物理研究所 | Alkaline zinc-iron flow battery |
| CN110998946A (en) * | 2017-08-04 | 2020-04-10 | 西门子股份公司 | Redox flow battery and method of operating a redox flow battery |
| CN109991128A (en) * | 2019-03-18 | 2019-07-09 | 浙江大学 | A kind of the optimization measurement method and device of all-vanadium redox flow battery system mass tranfer coefficient |
| CN109991128B (en) * | 2019-03-18 | 2020-03-17 | 浙江大学 | Optimized measurement method and device for mass transfer coefficient of all-vanadium redox flow battery system |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180277864A1 (en) | 2018-09-27 |
| WO2011126908A3 (en) | 2011-12-15 |
| US20130029187A1 (en) | 2013-01-31 |
| CN102823046B (en) | 2016-08-03 |
| US10008729B2 (en) | 2018-06-26 |
| CN106159189A (en) | 2016-11-23 |
| EP2553752A2 (en) | 2013-02-06 |
| WO2011126908A2 (en) | 2011-10-13 |
| US20110244277A1 (en) | 2011-10-06 |
| CN106159189B (en) | 2019-11-01 |
| US20140363707A1 (en) | 2014-12-11 |
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